CN114959754A - Device and method for efficiently preparing hydrogen and nickel compound - Google Patents

Device and method for efficiently preparing hydrogen and nickel compound Download PDF

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CN114959754A
CN114959754A CN202110206356.0A CN202110206356A CN114959754A CN 114959754 A CN114959754 A CN 114959754A CN 202110206356 A CN202110206356 A CN 202110206356A CN 114959754 A CN114959754 A CN 114959754A
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nickel
electrolyte
hydrogen
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cathode
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易志国
吴燕秋
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Shanghai Institute of Ceramics of CAS
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Shanghai Institute of Ceramics of CAS
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    • C—CHEMISTRY; METALLURGY
    • C25—ELECTROLYTIC OR ELECTROPHORETIC PROCESSES; APPARATUS THEREFOR
    • C25B—ELECTROLYTIC OR ELECTROPHORETIC PROCESSES FOR THE PRODUCTION OF COMPOUNDS OR NON-METALS; APPARATUS THEREFOR
    • C25B9/00—Cells or assemblies of cells; Constructional parts of cells; Assemblies of constructional parts, e.g. electrode-diaphragm assemblies; Process-related cell features
    • C—CHEMISTRY; METALLURGY
    • C25—ELECTROLYTIC OR ELECTROPHORETIC PROCESSES; APPARATUS THEREFOR
    • C25B—ELECTROLYTIC OR ELECTROPHORETIC PROCESSES FOR THE PRODUCTION OF COMPOUNDS OR NON-METALS; APPARATUS THEREFOR
    • C25B1/00—Electrolytic production of inorganic compounds or non-metals
    • C—CHEMISTRY; METALLURGY
    • C25—ELECTROLYTIC OR ELECTROPHORETIC PROCESSES; APPARATUS THEREFOR
    • C25B—ELECTROLYTIC OR ELECTROPHORETIC PROCESSES FOR THE PRODUCTION OF COMPOUNDS OR NON-METALS; APPARATUS THEREFOR
    • C25B1/00—Electrolytic production of inorganic compounds or non-metals
    • C25B1/01—Products
    • C25B1/02—Hydrogen or oxygen
    • C—CHEMISTRY; METALLURGY
    • C25—ELECTROLYTIC OR ELECTROPHORETIC PROCESSES; APPARATUS THEREFOR
    • C25B—ELECTROLYTIC OR ELECTROPHORETIC PROCESSES FOR THE PRODUCTION OF COMPOUNDS OR NON-METALS; APPARATUS THEREFOR
    • C25B1/00—Electrolytic production of inorganic compounds or non-metals
    • C25B1/01—Products
    • C25B1/24—Halogens or compounds thereof
    • C25B1/26—Chlorine; Compounds thereof
    • Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
    • Y02P—CLIMATE CHANGE MITIGATION TECHNOLOGIES IN THE PRODUCTION OR PROCESSING OF GOODS
    • Y02P20/00—Technologies relating to chemical industry
    • Y02P20/10—Process efficiency
    • Y02P20/133—Renewable energy sources, e.g. sunlight

Abstract

The invention relates to a device and a method for efficiently preparing hydrogen and nickel compounds, wherein the device for efficiently preparing the hydrogen and the nickel compounds comprises the following components: a neutral or acidic aqueous solution containing halogen element ions is used as an electrolyte; an anode and a cathode distributed in the electrolyte; and an external power supply for connecting the anode and cathode surfaces; the anode is metallic nickel; the cathode is a conductive material.

Description

Device and method for efficiently preparing hydrogen and nickel compound
Technical Field
The invention relates to a device and a method for efficiently preparing hydrogen and a nickel compound, belonging to the technical field of hydrogen production.
Background
H 2 Is a renewable energy source with environmental protection, abundant resources and high energy density, and is one of the best substitutes of fossil fuels. Production of H by using renewable solar energy to drive electrochemical water splitting 2 The green approach of fuel, hydrogen production by water electrolysis can be divided into two half reactions: oxygen Evolution Reaction (OER) at the anode and Hydrogen Evolution Reaction (HER) at the cathode, where OER involves a four electron process due to its slow natureAnd is an electron donor for HER, is considered to be a major bottleneck problem of high energy consumption for hydrogen production by water electrolysis. In order to reduce the energy consumption of hydrogen production by electrolysis, a high-efficiency reaction system needs to be found in principle, and the electromotive force of hydrogen production by water electrolysis is reduced.
Since the anode OER requires a large overpotential, and the anode product oxygen is not only of low value, but may also form an explosive mixture with hydrogen, causing a hazard. It is a feasible method to replace the oxygen evolution reaction with the oxidation reaction of another easily oxidizable substance, i.e., the anode easily oxidizable substance undergoes the oxidation reaction to provide an electron donor for the cathode hydrogen production reaction.
The nickel is a metal which is easy to be oxidized, theoretically, nickel can be oxidized in an electrochemical mode, nickel ions are obtained at the anode, hydrogen is obtained at the cathode, the theoretical standard electromotive force is 0.257V and is far lower than the reaction electromotive force (1.23V) of hydrogen and oxygen generated by electrolyzing water, and therefore the coupling of the nickel oxidation reaction and the hydrogen evolution reaction can realize electrolytic hydrogen production under lower energy consumption.
Disclosure of Invention
Aiming at the defects of the prior art, the invention aims to provide a stable and efficient device for preparing hydrogen and nickel compounds by nickel electrolysis and an electrolysis method.
In one aspect, the present invention provides an apparatus for efficiently producing hydrogen and a nickel compound, comprising:
a neutral or acidic aqueous solution containing halogen element ions is used as an electrolyte;
an anode (1) and a cathode (2) distributed in the electrolyte;
and an external power supply (5) for connection to the anode and cathode surfaces;
the anode is metallic nickel; the cathode is a conductive material (such as platinum, nickel, graphite, transition metal or composite materials thereof).
In the present disclosure, metallic nickel is connected to the positive electrode of a power supply, and a conductive material is connected to the negative electrode of the power supply, and both are placed in a neutral or acidic solution containing halogen element ions, and when the power supply is turned on, the metallic nickel is oxidized at the positive electrode to generate nickel ions, and the halogen element ions (for example, chloride ions and bromide ions) at higher concentrationEtc.) the oxidation process of the metallic nickel does not passivate. The oxidation reaction of metallic nickel improves the electron donor to the hydrogen production reaction of the cathode, and the hydrogen ions are reduced at the cathode to generate H 2 。
Preferably, the total concentration of the halogen element ions in the neutral or acidic aqueous solution containing the halogen element ions is not less than 0.1M. The conductive material is selected from at least one of platinum, nickel, graphite, and transition group metals (specific materials are not limited, and conductive is sufficient, and these are just examples).
The concentration of the halogen element ion in the electrolyte is preferably 0.5M to 5M, more preferably 1M to 5M, and still more preferably 3M to 5M.
Preferably, the precursor of the halogen element ion is at least one of potassium halide, sodium halide, HCl and HBr.
Preferably, the device further comprises a housing for containing the electrolyte.
Preferably, a first inlet (3 or 4) is provided on the side of the housing adjacent to the anode or/and cathode for the input of electrolyte.
Preferably, above the housing near the cathode, a first outlet (6) is provided for outputting H 2 (ii) a Or/and at least one second outlet (7) is arranged below the shell and used for outputting the electrolyte.
On the other hand, the invention provides a method for efficiently preparing hydrogen and nickel compounds, which adopts the device for efficiently preparing hydrogen and nickel compounds to realize the efficient preparation of hydrogen and nickel compounds by inputting current or voltage for reaction through an external power supply.
Preferably, the voltage is 0-3V. The current is 0.001-2A.
Preferably, the reaction temperature is 0-100 ℃; preferably, the reaction temperature is 25-70 DEG C
Has the advantages that:
the hydrogen production method has the advantages of simplicity, high efficiency and low power consumption, the oxygen evolution reaction relates to four-electron transfer, the nickel oxidation reaction is two-electron transfer, and the reaction product does not contain gas, so that the condition of active area loss caused by the fact that bubbles do not leave the surface of the electrode in time can be avoided. The invention utilizes the high-efficiency nickel oxidation reaction to replace the low-efficiency oxygen precipitation reaction in the water electrolysis process, reduces the voltage and energy consumption of the hydrogen production reaction by electrolysis, and is a good improvement on the conventional hydrogen production by water electrolysis;
the hydrogen production method can greatly reduce the production cost, when neutral solution containing halogen element ions is taken as electrolyte, nickel hydroxide byproducts can be generated besides hydrogen generated at the cathode, when acidic solution containing halogen element ions is taken as electrolyte, nickel halide byproducts can be obtained, and in addition, compared with the method for producing low-value oxygen by electrolyzing water, the method does not need to use an ion exchange membrane (separating hydrogen from oxygen).
Drawings
FIG. 1 is an XRD pattern of the green product of examples 1, 2 and 3, demonstrating that the green product is β -Ni (OH) 2 ；
In FIG. 2, a and b are beta-Ni (OH) prepared in example 1 2 The structural diagram of the SEM topography, and the b picture is a partial enlarged view of the a picture;
in FIG. 2, c and d are beta-Ni (OH) prepared in example 2 2 The structural diagram of the SEM topography of (1), wherein the diagram c is a partial enlarged view of the diagram d;
in FIG. 2, e and f are beta-Ni (OH) prepared in example 3 2 The structural diagram of the SEM topography is shown in a drawing e, and a partial enlarged view of the drawing f is shown in a drawing e;
FIG. 3 is a performance test of example 1, example 2, and example 3 in a two-electrode system, where a is the LSV curve and b is the system at 10mA cm -2 A constant current test result graph under the current density of (a);
FIG. 4 is the LSV curve test of example 4 under a two-electrode system;
FIG. 5 is the LSV curve test of example 5 under a two-electrode system;
FIG. 6 is the LSV curve test of example 6 under a two-electrode system;
FIG. 7 is a LSV curve test of comparative example 1 under a two-electrode system;
FIG. 8 is a LSV curve test of comparative example 2 under a two-electrode system;
FIG. 9 is a LSV curve test of comparative example 3 under a two-electrode system;
FIG. 10 is a LSV curve test of comparative example 4 under a two-electrode system;
FIG. 11 is a LSV curve test of comparative example 5 under a two-electrode system;
FIG. 12 is a LSV curve test of comparative example 6 under a two-electrode system;
FIG. 13 is a schematic view of an experimental apparatus.
Detailed Description
The present invention is further illustrated by the following examples, which are to be understood as merely illustrative and not restrictive.
In the method, the efficient nickel oxidation reaction is used for replacing the low-efficiency oxygen precipitation reaction in the water electrolysis process, so that the voltage and energy consumption of the hydrogen electrolysis reaction are reduced, and the method is a good improvement on the conventional water electrolysis hydrogen production.
In the invention, the device for preparing hydrogen and nickel compounds with high efficiency can be used for preparing hydrogen at the cathode and also can obtain nickel chemicals (such as nickel hydroxide or nickel chloride), and compared with low-value oxygen generated at the anode by electrolyzing water, the system does not need to use a diaphragm because oxygen is not generated, thereby further improving the problem of high production cost.
In the present invention, metallic nickel is connected to the positive electrode of the power supply. The electrolyte may be a neutral or acidic solution containing ions of a halogen element. The solute in the solution containing the halogen element ions can be at least one of sodium chloride, sodium bromide, potassium chloride, potassium bromide, HCl and HBr, and the total concentration of the halogen element ions is not less than 0.1M. In an alternative embodiment, the purity of the metallic nickel is greater than or equal to 80%.
In an optional embodiment, the concentration of the halogen ions in the neutral or acidic electrolyte is 0.5-5M, preferably 1-5M, and more preferably 3-5M. If the concentration is too low, the electrolyte content in the solution is low, the conductivity is poor, the solution resistance is high, and nickel has passivation behavior, so that higher voltage is required to achieve the same current density. If the concentration is too high, the concentration of saturated sodium chloride is about 5.1M at 25 ℃, the oxidation of nickel can not generate passivation behavior in a high-concentration sodium chloride solution, the higher the ion concentration is, the better the conductivity is, but if the ion concentration is too high, on one hand, the performance is not greatly improved, and sodium chloride can be separated out.
In one embodiment of the invention, the power is turned on and the reaction is carried out at a temperature and, after a period of time, hydrogen is collected at the cathode and nickel containing chemicals are collected at the anode. The reaction temperature can be 0-100 ℃. The reaction temperature is increased, so that the oxidation rate of the metal nickel on the anode can be further accelerated, and the hydrogen production rate and the hydrogen production quantity are facilitated.
The present invention will be described in detail by way of examples. It is also to be understood that the following examples are illustrative of the present invention and are not to be construed as limiting the scope of the invention, and that certain insubstantial modifications and adaptations of the invention by those skilled in the art may be made in light of the above teachings. The specific process parameters and the like of the following examples are also merely one example of suitable ranges, i.e., those skilled in the art can select the appropriate ranges through the description herein, and are not limited to the specific values exemplified below.
Example 1
A stable and efficient hydrogen production method by nickel electrolysis comprises the following steps:
(1) cutting 1cm × 1.5cm of foamed nickel, and ultrasonically cleaning with dilute hydrochloric acid, ethanol and deionized water for 10 minutes respectively for later use;
(2) preparing 4M sodium chloride as electrolyte, setting the temperature of the system to be 25 ℃, and setting the exposed area to be 1cm 2 The foamed nickel is connected with the anode of a power supply, 1cm 2 The platinum sheet is connected with the negative electrode of a power supply, voltage is applied, and hydrogen is collected at the platinum sheet. In addition, after the system reacts for a period of time, the green substances generated in the solution are placed for 12 hours, then are washed and centrifuged, and finally are dried in vacuum at 60 ℃ for 6 hours.
Example 1 was characterized as follows:
(1) XRD analysis and morphology analysis: XRD pattern of green product obtained in example 1 as shown in figure 1, by comparison to PDF card (. beta. -Ni (OH)) 2 ) It is seen that it is consistent with the results shown in FIG. 1, whichThe by-product of the system is beta-Ni (OH) 2 (ii) a beta-Ni (OH) obtained in example 1 2 The SEM image of FIG. 2 is shown as a, and the enlarged view b shows that the product is composed of a plurality of flocculent substances;
(2) performance and stability testing: FIG. 3 a is the LSV curve obtained from the test of example 1, and it can be seen that the current density reaches 50mA cm -2 When the hydrogen production system is used, the overall system potential is only 1.31V, and the excellent hydrogen production performance is shown; in FIG. 3, b is 10mA cm for example 1 -2 The result of constant current test at a current density of 10mA cm can be seen -2 The potential of the system can be stabilized at 1.02V within 1.5 h.
Example 2
The process for efficiently producing hydrogen and a nickel compound in example 2 is substantially the same as in example 1 except that: the temperature of the reaction system was 50 ℃.
Example 2 was characterized as follows:
(1) XRD analysis and morphology analysis: the XRD pattern of the green product obtained in example 2 is shown in FIG. 1 by comparison with PDF card (. beta. -Ni (OH)) 2 ) It is seen that the by-product of this system is β -Ni (OH) 2 beta-Ni (OH) obtained at this temperature 2 Than beta-Ni (OH) obtained at 25 deg.C 2 The diffraction peak is sharp; beta-Ni (OH) obtained in example 2 2 The SEM image of fig. 2 c, in combination with the magnified image d, shows that the product consists of many pills;
(2) performance and stability testing: FIG. 3 a is the LSV curve obtained from the test of example 2, and it can be seen that the current density reaches 50mA cm -2 When the hydrogen production device is used, the overall system potential is only 1.15V, and excellent hydrogen production performance is shown; in FIG. 3, b is 10mA cm in the sample 2 -2 The result of the constant current test at the current density of (2) is shown in the figure, and it can be seen that when the current density is 10mA · cm -2 The potential of the system can be stabilized at 0.87V within 1.5 h.
Example 3
The process for efficiently producing hydrogen and a nickel compound in example 3 is substantially the same as in example 1 except that: the temperature of the reaction system was 70 ℃.
Example 3 was characterized as follows:
(1) XRD analysis and morphology analysis: the XRD pattern of the green product obtained in example 3 is shown in figure 1, the temperature at which beta-Ni (OH) is obtained 2 Than beta-Ni (OH) obtained at 50 DEG C 2 The diffraction peak is sharper. beta-Ni (OH) obtained in example 3 2 E in fig. 2, in combination with the enlarged view f, it can be seen that the morphology of the product is a pompon consisting of a plurality of platelets.
(2) Performance and stability testing: FIG. 3 a is the LSV curve obtained from the test of example 3, and it can be seen that the current density reaches 50mA cm -2 When the hydrogen production system is used, the overall system potential is only 1.03V, and the excellent hydrogen production performance is shown; in FIG. 3, b is 10mA cm in the sample 3 -2 The result of the constant current test at the current density of (2) is shown in the figure, and it can be seen that when the current density is 10mA · cm -2 The potential of the system can be stabilized at 0.70V within 1.5 h.
Example 4
A stable and efficient hydrogen production method by nickel electrolysis comprises the following steps:
(1) cutting 1cm × 1.5cm of foamed nickel, and ultrasonically cleaning with dilute hydrochloric acid, ethanol and deionized water for 10 minutes respectively for later use;
(2) preparing 2M hydrochloric acid as electrolyte, setting the temperature of the system to be 25 ℃, and setting the exposed area to be 1cm 2 The foamed nickel is connected with the anode of a power supply, 1cm 2 The platinum sheet is connected with the negative electrode of a power supply, voltage is applied, and hydrogen is collected at the platinum sheet. In addition, after the system reacts for a period of time, the green solution is evaporated and crystallized to obtain the nickel chloride product.
And (3) performance testing:
FIG. 4 is the LSV curve obtained from the test of example 4, and it can be seen from the graph that the current density reached 500mA cm when the current density reached -2 And when the hydrogen production is carried out, the overall system potential is only 0.91V, and the excellent hydrogen production performance is shown.
Example 5
A stable and efficient hydrogen production method by nickel electrolysis comprises the following steps:
(1) cutting 1cm × 1.5cm of foamed nickel, and ultrasonically cleaning with dilute hydrochloric acid, ethanol and deionized water for 10 minutes respectively for later use;
(2) preparing 1M sodium chloride as electrolyte, setting the temperature of the system to be 25 ℃, and setting the exposed area to be 1cm 2 The foamed nickel is connected with the positive electrode of a power supply by 1cm 2 Platinum sheet or 1cm 2 The nickel foam is connected with the negative pole of a power supply, voltage is applied, and hydrogen is collected at the platinum sheet or the nickel foam. In addition, after the system reacts for a period of time, the green substances generated in the solution are placed for 12 hours, then are washed and centrifuged, and finally are dried in vacuum at 60 ℃ for 6 hours.
And (3) performance testing:
FIG. 5 is the LSV curve obtained from the test of example 5, and it can be seen from the graph that when the current density reaches 10 mA-cm at the current density using foamed nickel as the anode material -2 When the potential of the total system with the conductive material platinum as the cathode is 1.14V, and the potential of the total system with the conductive material nickel foam as the cathode is 1.26V.
Example 6
A stable and efficient hydrogen production method by nickel electrolysis comprises the following steps:
(1) cutting 1cm × 1.5cm of foamed nickel, and ultrasonically cleaning with dilute hydrochloric acid, ethanol and deionized water for 10 minutes respectively for later use;
(2) preparing saturated sodium chloride as electrolyte, setting the temperature of the system at 25 ℃, and setting the exposed area at 1cm 2 The foamed nickel is connected with the positive electrode of a power supply by 1cm 2 Platinum sheet or 1cm 2 The nickel foam is connected with the negative pole of a power supply, voltage is applied, and hydrogen is collected at the platinum sheet or the nickel foam. In addition, after the system reacts for a period of time, the green substances generated in the solution are placed for 12 hours, then are washed and centrifuged, and finally are dried in vacuum at 60 ℃ for 6 hours.
And (3) performance testing:
FIG. 6 is the LSV curve obtained from the test of example 6, and it can be seen from the graph that when the current density reaches 10 mA-cm at the current density using foamed nickel as the anode material -2 When the potential of the overall system with the conductive material platinum as the cathode is 1V, and the potential of the overall system with the conductive material nickel foam as the cathode is 1.09V.
Comparative example 1
A stable and efficient hydrogen production method by nickel electrolysis comprises the following steps:
(1) cutting 1cm × 1.5cm of foamed nickel, and ultrasonically cleaning with dilute hydrochloric acid, ethanol and deionized water for 10 minutes respectively for later use;
(2) 0.1M sodium chloride is prepared as electrolyte, the temperature of the system is set to be 25 ℃, and the exposed area is 1cm 2 The foamed nickel is connected with the positive electrode of a power supply by 1cm 2 The platinum sheet is connected with the negative electrode of a power supply, voltage is applied, and hydrogen is collected at the platinum sheet. In addition, after the system reacts for a period of time, the green substances generated in the solution are placed for 12 hours, then are washed and centrifuged, and finally are dried in vacuum at 60 ℃ for 6 hours.
And (3) performance testing:
FIG. 7 is the LSV curve obtained by the test of comparative example 1, from which it can be seen that the current density reached 10mA cm -2 The overall system potential is 1.75V.
Comparative example 2
Preparing saturated sodium chloride (5.1moL) as electrolyte, setting the system temperature to 25 ℃, and respectively setting the exposure area to 1cm 2 The platinum sheet is connected with the positive electrode and the negative electrode of a power supply, voltage is applied, hydrogen is collected at the cathode, and chlorine can be collected at the anode.
And (3) performance testing:
FIG. 8 is the LSV curve obtained by the test of comparative example 2, from which it can be seen that the current density reached 10mA cm -2 The overall system potential is 2.17V.
Comparative example 3
Preparing saturated sodium sulfate (0.3g/mL) as electrolyte, setting the system temperature at 25 ℃, and respectively setting the exposure area at 1cm 2 The platinum sheet is connected with the positive electrode and the negative electrode of a power supply, voltage is applied, hydrogen is collected at the cathode, and oxygen can be collected at the anode.
And (3) performance testing:
FIG. 9 is the LSV curve obtained by the test of comparative example 3, from which it can be seen that the current density reached 10mA cm -2 The overall system potential is 2.9V.
Comparative example 4
Preparation of saturated sulfurSodium acid (0.3g/mL) was used as an electrolyte, the system temperature was set to 25 ℃ and the exposed area was 1cm 2 The foamed nickel is connected with the positive electrode of a power supply by 1cm 2 The platinum sheet is connected with the negative electrode of a power supply, voltage is applied, hydrogen is collected at the platinum sheet, and oxygen can be collected at the nickel foam.
And (3) performance testing:
FIG. 10 is the LSV curve obtained by the test of comparative example 4, from which it can be seen that the current density reached 10mA cm -2 The overall system potential is 2.41V.
Comparative example 5
Preparing 2M HCl as electrolyte, setting the temperature of the system to be 25 ℃, and respectively setting the exposure area to be 1cm 2 The platinum sheet is connected with the positive electrode and the negative electrode of a power supply, voltage is applied, hydrogen is collected at the cathode, and chlorine can be collected at the anode.
And (3) performance testing:
FIG. 11 is the LSV curve obtained by the test of comparative example 5, from which it can be seen that the current density reached 10mA cm -2 The overall system potential is 1.38V.
Comparative example 6
Configuration 1M H 2 SO 4 As an electrolyte, the temperature of the system was set to 25 ℃ and the exposed area was 1cm each 2 The platinum sheet is connected with the positive electrode and the negative electrode of a power supply, voltage is applied, hydrogen is collected at the cathode, and oxygen can be collected at the anode.
And (3) performance testing:
FIG. 12 is the LSV curve obtained by the test of comparative example 6, from which it can be seen that the current density reached 10mA cm -2 The overall system potential is 2.04V.
Table 1-1 shows the effect of different anode reactions on hydrogen generation performance:
Figure BDA0002950896300000081
tables 1-2 show the effect of different anode reactions on hydrogen generation performance:
Figure BDA0002950896300000082
table 2 shows the effect of different reaction temperatures on the hydrogen production performance of the reaction system:
Figure BDA0002950896300000083
Figure BDA0002950896300000091
table 3 shows the effect of different sodium chloride concentrations on the hydrogen production performance of the reaction system
Figure BDA0002950896300000092
Under neutral condition, the invention uses metallic nickel as the anode of the electrolysis device, and the solution containing halogen element ions as the electrolyte, when voltage is applied, the anode generates nickel oxidation reaction, and the cathode generates water reduction, thereby obtaining hydrogen and byproduct-nickel hydroxide. As can be seen from Table 1, the oxidation of nickel is more efficient than the anodic generation of the oxidation of chloride ions (anodic product: chlorine) and the oxidation of water (anodic product: oxygen), in particular by requiring a smaller applied voltage to achieve the same current density, which means that only a very low voltage needs to be applied to drive the overall reaction.
The temperature and the concentration of the halogen ions in the electrolyte play a decisive role in the reaction system according to the invention. The oxidation reaction of nickel occurs more easily with an increase in the concentration of the halogen element ions or an increase in the temperature of the electrolyte, and the smaller the voltage to be applied to achieve the same current density means that the lower the electric power to be consumed for obtaining the same volume of hydrogen gas, and in addition to this, the higher the crystallinity of the by-product (nickel hydroxide) to be obtained with an increase in the temperature.
Under acidic conditions, the invention uses metallic nickel as the anode of the electrolysis device, and uses an acidic solution containing halogen element ions as the electrolyte, and when a voltage is applied, the oxidation reaction of nickel occurs at the anode, which is more efficient than the oxidation of chlorine ions (anode product: chlorine gas) and the oxidation of water (anode product: oxygen gas) under neutral conditions.
Although embodiments of the present invention have been shown and described above, it is understood that the above embodiments are exemplary and should not be construed as limiting the present invention, and that variations, modifications, substitutions and alterations can be made in the above embodiments by those of ordinary skill in the art without departing from the principle and spirit of the present invention.

Claims (10)

1. An apparatus for efficiently producing hydrogen gas and a nickel compound, comprising:
a neutral or acidic aqueous solution containing halogen element ions is used as an electrolyte;
an anode and a cathode distributed in the electrolyte;
and an external power supply for connecting the anode and cathode surfaces;
the anode is metallic nickel; the cathode is a conductive material.
2. The apparatus of claim 1, wherein the conductive material is selected from at least one of platinum, nickel, graphite, and a transition group metal.
3. The device according to claim 1 or 2, wherein the total concentration of the ions of the halogen element in the electrolyte is not less than 0.1M, preferably the total concentration of the ions of the halogen element in the electrolyte is 1M to 5M, more preferably 3M to 5M.
4. The apparatus of any of claims 1-3, wherein the precursor of the halide ion is at least one of potassium halide, sodium halide, HCl, HBr.
5. The device of any one of claims 1-4, further comprising a housing for containing an electrolyte.
6. A device according to claim 5, wherein a first inlet is provided for the input of electrolyte at a side of the housing adjacent the anode or/and the cathode.
7. A device according to claim 5 or 6, characterized in that above the casing near the cathode, a first outlet is provided for the output H 2 (ii) a Or/and a second outlet is arranged below the shell and used for outputting the electrolyte.
8. The method for efficiently preparing the hydrogen and the nickel compound is characterized in that the device for efficiently preparing the hydrogen and the nickel compound, which is disclosed by any one of claims 1 to 7, is adopted to carry out reaction by inputting current or voltage through an external power supply so as to realize the efficient preparation of the hydrogen and the nickel compound.
9. The method according to claim 8, wherein the voltage is 0-3V; the current is 0.001-2A.
10. The process according to claim 8 or 9, characterized in that the temperature of the reaction is between 0 and 100 ℃.
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